Nu-substituted melamines



United States Patent 3,290,307 N-SUBSTITUTED MELAMINES Ernst Keller, Binningen, near Basel, and Joachim Dazzi, Riehen, near Basel, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed Jan. 3, 1963, Ser. No. 249,120 Claims priority, application Switzerland, July 7, 1961, 8,130/ 61 8 Claims. (Cl. 260--249.6)

lowering the congealing point, high pressure additives and/ or anticorrosives. The invention also concerns processes for the lubrication or hydraulic-propulsion of ma- ,chines or parts thereof as well as new melamine derivatives which can be used as lubricating agents and/or hydraulic liquids.

Very high demands with regard to heat stability are :made of synthetic lubricating agents and hydraulic liquids such as are necessary, for example, in turboprop aero en- .gines or the modern high temperature apparatus in mechanical and electrical industries.

For use in engines operating at high temperatures such as turboprop aero engines, synthetic lubricating agents must, in the first place, fulfill the following conditions:

(1) They must be capable of forming a lubricating film on the most various metals;

(2) They must be only slightly volatile and have substantial stability to heat;

(3) They should not have a corrosive action and, above all, they should not form acid decomposition products;

(4) .T hey should retain their lubricating properties over as wide a temperature range as possible, i.e. their Viscosity should be as little dependent as possible on temperature;

(5) They should have, in addition to these properties, on the one hand as low a solidification point as possible and on the other as high a boiling point as possible.

It is difficult to find substances which fulfill these demands to such an extent that they can be employed, for example, as lubricants for turboprop aero engines. The usual lubricants do not fulfill the demands of modern motors, in particular of turboprop aero engines; those of an ester basis because of their volatility and heat stability and those of a hydrocarbon basis because of their volatility, their solidification point and the dependence of their viscosity on temperature (ASTM slope).

It has now surprisingly been found that certain melamines suitably substituted at the nitro atom of the amino groups have the properties required above and thus can be used as hydraulic liquids when high demands are made and as synthetic lubricants for a particularly wide range of temperatures.

The melamines preferred according to the invention are compounds of the formula wherein 3,290,307 Patented Dec. 6, 1966 "ice Y is a di-(lower alkyl) -amino group in which each alkyl radical has from 1 to 4 carbon atoms R is hydrogen or alkyl of maximally 14 carbon atoms R is an alkyl group of at least 6 and maximally 18 carbon atoms or a cycloliexyl group,

the sum of the total number of alkyl carbon atoms in R and R being at least 8 and not more than 28 when R is alkyl, and R and R taken together can be either Very interesting as lubricants on account of their good ASTM slope which is below 0.8, are the compounds of the above Formula I in which there are a total of five alkyl substituents at the three amino-nitrogen atoms, one of which substituents is an alkyl group with 18 carbon atoms.

Another subclass of compounds which are particularly interesting in view of their good lubricant properties, (ASTM slope in the order of 0.7 and lower, and weight loss at 380 C. below 6%) are those compounds of the above Formula I in which there are a total of six substituent alkyl groups at the three amino-nitrogen atoms, and wherein one of these alkyl groups has from 12 to 18 carbon atoms.

The invention further relates to a method of lubricating a substrate with a compound of the above Formula I, and to compositions which contain the aforesaid compounds as essential ingredients.

Apart from substituted, particularly alkyl-substituted amino groups, the nitrogen substitutents of melamines useable according to the invention must not contain any functional groups. In particular they contain no acid, salt-forming substituents or any which can be converted into such; for example, they contain neither sulphonic acid groups nor carboxyl, sulphonic acid ester, carboxylic acid ester, sulphamyl, carbamoyl, nor cyano groups.

If two substituents of the same nitrogen atom are bound in ring form then, they form, for example, the pyrrolidine, piperidine, morpholine, hexamethyleneimine, N-alkylpiperazine ring.

The N,N',N"-substituted melamines according to the invention, are easily produced by reacting in steps, by known methods, the three chlorine atoms of cyanuric chloride with primary or secondary organic amines.

In the first and/or second step, less easily reacting amines are reacted and in the third step those which rehydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene or dichlorobenzene, in the presence of acid binding agents at suitable temperatures. Exam- ,ples of acid binding agents are the alkali metal salts of .low fatty acids such as sodium acetate, also those of weaker polybasic acids such as sodium or potassium carbonate, sodium or potassium hydrogen carbonate and, in suitable amount and form, also alkali hydroxides as well as tertiary nitrogen bases such as triethylamine, triethanolamine, pyridine, etc. The first chlorine atom of the cyanuric chloride is reacted advantageously at a low temperature up to 15 C., the second chloride atom is reacted at medium temperatures up to 60 C. and the third chlorine atom is reacted, if necessary, at higher temperatures, an excess of amine being used advantageously as acid binding agent. Aliphatic amines which can be used, for example, are primary and secondary amines containing normal and/or branched chain alkyl groups of 1 to 18 carbon atoms, or alkoxyalkyl groups of 3 to 20 carbon atoms, or aminoalkyl groups have advantageously a tertiary amino group, e.g. a dialkylamino, diaralkylarnino, dicycloalkylamino, alkylaralkylamino, alkylarylamino, polymethyl- .eneimino, morpholino or N'-alkylpiperidino group. As

alicyclic amines can be used, for example, cyclopentylamine, cyclohexylamine, 'and cycloheptylamine, dihydroabietinylamine and examples of secondary amines of this series are the corresponding bis-alicyclic amines or also secondary alkyl-cycloalkyl, aralkylcycloalkyl or phenylcycloalkyl amines.

The crude N,N',N"-substituted melamines according to the invention can contain mixtures of primary, secondary and tertiary amines which must be removed by purification as described hereinafter. Because of their great stability to heat, they can easily be obtained in pure form by distillation. The melamine derivatives can also be purified by extraction with a selective solvent such as acetic acid, by treatment with a bleaching earth such as Tonsil AC or an adsorption earth such as Celite PC or with an ion-exchanger such as Amberlite IR 120.

The N,N',N"-substituted melamines used according to the invention are only slightly volatile oils or of fatty or wax-like consistency and they are distinguished by high thermostability as they decompose to a harmful degree only at temperatures over 380 C. In this respect they have the advantage over the best products hitherto in commercial use for this purpose, namely the triesters of higher fatty acids with trimethylolpropane; these cannot be used at temperatures of over 320 C. In addition, the lubricants and hydraulic liquids according to the invention are more stable to hydrolysis than lubricants of an ester basis used up to now.

Also, even under extreme test conditions such as are laid down for turboprop aero engines, they hardly form any acid decomposition products. Thus, for example, the volatile compounds formed from 2-diethylamino-4-dibutylamino-6-dode-cylamino-1,3,5-triazine (compare compound No. 1 in the following Table I), and also the residue have an acid value of only 1 mg. KOH/g. or 0.7 mg. KOH/g. respectively after 6 hours exposure to a temperature of 380 C., i.e. both the volatile compounds as Well as the residue formed from compound No. 1 of Table I are neutral for all practical purposes after several hours exposure to heat Whereas the volatile substances formed from trimethylolpropane tripelargonate under the same conditions have an acid value of 117.3 mg. KOH/g.

In addition, the flash point of the melamines useable according to the invention is favorable. It was determined according to the ASTM designation: D 93-58 T (The American Society for Testing Materials, 1915 Race St., Philadelphia 3, Pa.). In the case of compound No. 1 of Table I mentioned above, it is above 300 C. and is thus higher than that of the sebacates of alkanols, now in commercial use.

Also the density of the melamines useable according to the invention is favorable, for example that of compound No. 1 on the following Table I is only about 0.88 and that of compound No. 16 in the same table is only 0.85. The densities of the conventional lubricants of an ester are higher.

The melamines according to the invention are distinguished over the previously known substances recommended as lubricants for turboprop engines such as e.g.

the ortho-phosphoric acid esters of organic hydroxyl compounds, by their much slighter corrosive action, they are distinguished over the esters of higher polycarboxylic acids with polyalcohols by their less pronounced swelling action on synthetic materials such as, e.g. on high molecular copolymers from butadiene and acrylonitrile (e.g. Hycar 38, made by Messrs. Goodrich in Akron, Ohio, U.S.A.), and they are distinguished over esters from pentaerythrite and monocarboxylic acids of medium chain length by the above-mentioned higher heat stability. They are also distinguished over all these known lubricants in that, having good proper-ties at low temperatures, they are very stable particularly at high temperatures. In addition, they are distinguished over the silicone oils, some of which are also thermostable, by their better lubricating proper- 'ties and they-are distinguished over polyphenyl ethers by their lower solidification point and, therefore, their usefulness in the usual modern motors. The very good stability to acid and alkali of the melamine derivatives used according to the invention is also remarkable. In the liquid state, these melamine derivatives have medium to high viscosity; their great advantage lies in the fact that this viscosity is only slightly dependent on temperature.

The melamines useable according to the invention can be employed as lubricants in many ways. Properties desirable for a particular purpose can also be attained by the production of suitable mixtures of these melamines.

Thus, the melamines useable according to the invention are suitable for the lubrication of hard surfaces because, on contact with these surfaces, they form very adhesive surface films, e.g. they are suitable for lubricating the surface of metals as well as alloys thereof, the surfaces of silicates such as, e.g. glasses as well as of other materials needing lubrication such as, e.g. rubber washers.

The N,N,N"-substituted melamines useable according to the invention can be employed alone or they can also contain additives. Thus, when they are to be used at temperatures of over C., to make use of their favourable stability to heat they are mixed advantageously with antioxidants in order to hinder the auto-oxidation which sets in above this temperature. The amount of antioxidant is about 0.01 to 5% of the melamine.

Of the amines, which can be used as antioxidants in general the secondary monoamines, particularly the diarylamines having homoand hetero-cyclic radicals as well as the aromatic diamines, the amine substituents, preferably secondary, of which are in the ortho or, advantageously the para-positions are particularly valuable.

Examples of hom'ocyclic and heterocyclic aromatic diaryl amines which can be used as antioxidants are diphenylamines, phenylnaph-thylamines, phenylacenaphthenylamines; 4,4 diaphthylaminodiphenyl; thiazolyl (2)- naphthylamines; examples of aromatic diamines are N,N'- diphenyl p phenylenediamine, N,N dioctyl p phenylenediamine, N,N' dicyclohexyl p phenylenediamine, N sec. butyl N phenyl p phenylenediamine, N,N- bis -aminopropyl) -p-phenylenediamine.

Of the hydroxyl-substituted aromates which are employed particularly at not too high temperatures (i.e., under 200300 C. depending on type and substratum), as antioxidants those having a sterically hindered hydroxyl group as well as the derivatives of dihydroxyaryl compounds the hydroxyl groups of which are in oor pposition to each other, are suitable. Examples of particularly valuable compounds which can be used are the monophenol derivatives such as 2,4-dimethyl-6-tert. butylphenol, 2,6 di-tert. butyl-4-ethylphenol, 2,6-bis-(l'- methylcyclohexyl)-4-methylphenol, 2,6-di-tert. butyl-4- dimethyl aminomethyl phenol, 2,2 methylene-bis-(4- methyl-6-tert. butyl phenol), 2,2-thio-bis-(4-methyl-6- tert. butylphenol), 4,4'-dihydroxy-2,2-dimethyl-5,5'-ditert. butyl-diphenyl sulphide and diphenyl disulphide, 2, 6 bis (2'-hydroxy-3'-tert. butyl-5-methylbenzyl)-4- methylphenol, 1,1,3 tris-(4'-hydroxy-5'-tert. butyl-2'- methylphenyl)-butane, derivatives of polynuclear phenols such as 2-tert. butyl-l-hydroxynaphthalene, 4,6-di-tert. butyl 5-hydroxyindane, 5-hydroxyacenaphthene, polyvalent phenols and derivatives thereof: butyl pyrocatechin, octyl gallate, hydroquinone, butylhydroxy anisole, hydroquinone monobenzyl ether.

Of the aminohydroxyaryl compounds, as antioxidants those derivatives in which the amino and hydroxyl groups are in p-position to each other are particularly suitable. Examples are: p hydroxy-diphenylamine, plrydroxyoctyl aniline, p-hy-droxy-N-y-aminopropyl ani- 'me.

Of the heterocyclic compounds, which can be used as antioxidants the cylic imides are the best known; in addition however, also heterocyclic compounds having no nitrogen can be employed insofar as they are not included in the class of heterocyclic amines. Examples are: phenothiazine, 6-methoxyor 6-ethoxyor 6-ethylamino-2,2,4-trimethyl-1,2-dihydroquinoline or telomers thereof, 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline or tocopherol.

Didodecyl selenide may also be used as antioxidant.

In addition, the N,N',N"-substituted melamines useable according to the invention can also contain high pressure additives such as phosphites, phosphates, sulfonated oil etc., barium or calcium mahogany sulfonates, anti-corrosives such as sarcosines or benzotriazoles, agents lowering the solidification point and, possible, also anti-foaming agents such as the ones based on silicones.

In addition, the invention also embraces lubricating greases made from the melamine derivatives used according thereto by the addition of the usual thickeners. Examples of such thickeners are metal soaps, bentonite, phthalocyanines, violanthrones etc. I

The new synthetic lubricants can also be mixed with other lubricants, for example, with highly purified mineral oil fractions or with the so-called synthetic ester lubricants, i.e., esters of from 18 to 50 carbons atoms,

(a) Of fatty acid with alkane-triand tetra-01s containing from 4 to carbon atoms, and containing not more than one oxygen atom attached to each carbon atom, such as w-trimethylol alkanes,

(b) Those of alkanedicarboxylic acids containing 4 to 14 carbon atoms with alkanols, and

(c) Complex esters comprising the neutral esterification products of the above-defined polyhydric alcohols such as trimethylolpropane and pentaerythritol with a mixture of alkanoic acids as defined above, with the molar ratio of the polyhydric alcohol and the alkanedicarboxylic acid ranging from 4:1 to 1.33:1; and further with esters of ortho-silicic acid with 2-ethylhexanol, and with silicones or lubricants containing organic phosphorus compounds.

These additives can be used in any ratio advisable for the purposes intended in correspondence with the miscibility diagram of the two components. Preferred is a content of 5 to 95% by weight of the lubricant compounds defined in Formula I above, the balance consisting of one of the above-mentioned conventional lubricants. 1

The following examples illustrate the particular suitability of the N,N',N"-substituted melamines according to the invention for use as synthetic lubricants, as hydraulic liquids as well as oils for turboprop engines. Measurements are given therein according to the metric system and the temperatures are in degrees centigrade. Where mm. or mm. pressure are used in the examples torr (mm. Hg) is meant.

Example 1.2-diethylamino-4-dibulylamin0-6- dodecylamino-s-triazine A mixture consisting of 157 parts of 2-diethylamino-4- dibutylamino-6-chloro-s-triazine, 115 parts of dodecylamine and 31.2 parts of pulverised sodium hydroxide are carefully heated at 100 while stirring. The whole is then stirred for 5 hours at 120, diluted with 170 parts of a mixture of xylene isomers and refluxed for another 4 hours. Sodium chloride and excess caustic soda are then filtered 0a and the filtrate is Washed with water and then distilled. After distilling off the xylene, the residue is distilled in a high vacuum. At 205-07 under 0.02 mm. pressure, 208 parts of a thinly liquid mass are obtained. Its refraction index is 11 1.4980 and at 30 to 40 it is still clear and flowing.

Analysis.-C H N M.W. 462, calculated: C, 70.10

6 percent; H, 11.70 percent; N, 18.20 percent. Found: C, 69.99 percent; H, 11.51 percent; N, 18.73 percent.

The same end product is also obtained if, instead of sodium hydroxide, potassium hydroxide or a mixture of these two hydroxides is used. A great excess of dodecylamine can replace the sodium hydroxide.

Because it is still a clear, flowing liquid at -30 to 40, and because of its slight volatility, its very high boiling point and its great thermal stability, this compound either alone or combined with analogous compounds having similar properties is suitable as a hydraulic liquid and as lubricant under extreme conditions, for example in aero engines.

Example 2.2-diethylamino-4-dibutylamino-6-0ctadecylamino-s-triazine A mixture consisting of 119 parts of 2-diethylamino-4- dibutylamino-6-chloro-s-triazine (B.P. mm 138, r1 1.5142), 112 parts of octadecylamine and 20 partsof pulverised sodium hydroxide is stirred for 1 hour at and for 4 /2 hours at The mixture is then diluted with 170 parts of xylene and stirred for another 6 hours under reflux. After filtering ofl organic components and washing the filtrate with water, the solvent and excess amine are fractionally distilled at a pressure of 0.2 mm. and then heated for another hour at 240 bath temperature under 0.02 mm. The residue, 194 parts, is a colourless oil having a refraction index n =1.5055; it crystallises at 30. The yield is 93.5% of the theoretical.

Analysis. C H N calculated: C, 72.7%; H, 12.10%; N, 15.49%. Found: C, 72.96%; H, 12.31%; N, 15.22%.

This melamine derivative is very thermostable; it is also only slightly volatile at very high temperatures; it is very viscous and the viscosity is only relatively slightly dependent on the temperature. For example, the viscosity measured at 98.8, after 6 hours heating at 380, only changes by 0.7%. Because of these properties this compound is an excellent lulbricant.

Example 3.2,4-bis-dibutylamino-6-hexamethyleneiminos-triazine H9C4-N-C 4H9 H204 N N oHPoHFoHz A mixture consisting of 109.5 parts of 2,4-bis-dibutylamino 6-chloro-s-triazine, 39.6 parts of hexamethyleneimine and 15.2 parts of pulverised sodium hydroxide is stirred while cooling. After a half hour it is heated to 120, parts of xylene are added and the whole is stirred for another 9 hours at this temperature. The usual working up and distillation produced 121 parts of a colourless oil, the main fraction boiling at 178180 under 0.002 mm. pressure. Refraction index 11 1.5123; yield: 93.5% of the theoretical.

Analysis.C H N M.W. 432, calculated: C, 69.5%; H, 11.12%; N, 19.44%. Found: C, 69.73%; H, 11.23%; N, 19.40%.

This melamine derivative is a viscous liquid which solidifies at -57 and is only slightly volatile and very thermosta ble. It is therefore suitable as hydraulic liquid for extreme working conditions and as lubricant.

7 Example 4 45 parts of 2,4-bis-(di-n-butylamino)-6-piperidino-1,3, 5-triazine (Table I, No. having a viscosity of 15.17 centistokes at 98.8 and 55 parts of a highly purified mineral oil (Regal Oil B) are stirred together. The mixture has the good lubricating properties of the component and the viscosity of the mixture is 7.32 centistokes at 988.

The application range of the melamine compound used is considerably broadened by this reduction of the viscosity in that, for example, the mixture can be used, e.g. as power transmitting agent in parts of machines which are temporarily exposed to lower temperatures then usual. Under such conditions, the melamine derivative alone is less suitable for use.

Lubricant compositions having an extended range of uses are obtained in the same manner with melamine derivatives of relatively high viscosity such as, e.g. the compounds Nos. 8, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25 and 27 in Table I by mixing them in any ratio desired according to the intended use with Regal Oil B.

Example 5 80 parts of 2 diethylamino-4-di-n-butylamino-6-dihexylamino-1,3,5-triazine (Table I, No. 13) and 20 parts of sebacic acid di-2-ethylhexanol ester. The mixture has the good lubricant properties of the components and a viscosity of 7.13 centistokes in comparison to 9.98 centistokes at 988 of the melamine derivative used alone.

On reducing the viscosity by mixing with synthetic lubricants of an ester basis the application range of melamine derivatives useable according to the invention is broadened in that such mixtures can be used, e.g. as power transmission agents, in machines which are temporarily exposed to lower temperatures than usual.

In the same way, lubricant compositions having ratios of components as desired for the intended use can be produced with the other melamine derivatives given in Table I and the diesters of sebacic acid, azelaic acid, adipic acid etc., with alkanols having, e.g. 6 to 10 carbon atoms, esters of higher fatty acids of polyalcohols, in particular triesters of w-trimethyl-olalkanes and also higher molecular complex esters of dicarboxylic acids, polyalcohols, in particular trimethylolpropane and alkanoic acids defined hereinbefore, so that the mixtures have the viscosity desirable for the type of application.

Example 6 Centistokes At 98.8 19.6 At 37.8" 78.34

In the same way, lubricant compositions having a ratio of components as desired and having viscosity properties desired for the intended use can be produced with the other melamine derivatives given in Table I and silicone oils.

Example 7 6.5 parts of 2,4-bis-dibutylamino-6-ditetradecylamino- 1,3,5-triazine (Table I, No. 18) are stirred with 35 parts of sebacic acid di-Z-ethyl-hexanol ester. This mixture has a viscosity of 46.90 centistokes at 37.8 and 7.74 centistokes at 98.8". ASTM slope 0.64.

If, in the above example, instead of 35 parts of sebacic acid di-2-ethyl-hexanol ester, 35 parts of dinonyl adipate are used, then a mixture is obtained which has a viscosity 8 of 49.36 centistokes at 37.8 and 7.95 centistokes at 98.8 ASTM slope: 0.66.

Example 8 60 parts of 2,4-bis-dibutylamino-6-ditetradecylamino- 1,3,5-triazine (Table I, No. 18) and 40 parts of the triester of caprylic acid and 1,1,1-trimethylol propane are stirred together. This mixture has a viscosity of 51.86 centistokes at 988 and 8.13 centistokes at 98.8. ASTM slope: 0.66.

Example 9 55 parts of 2,4-bis-dibutylamino-6-ditetradecylamino- 1,3,5-triazine (Table I, No. 18) are stirred with 45 parts of the triester of pelamgonic acid and 1,1,1-trimethylolpropane. This mixture has a viscosity of 53.21 centistokes at 37.8 and 8.32 centistokes at 98.8. ASTM slope: 0.66.

Example 10 3 parts of copper phthalocyanine are stirred in 25 volume parts benzene in an Ultrafurax mixing apparatus (Jan'ke & Kunkel, Stauffen, Baden, Western Germany). 9 parts of 2-diethylamino-4dibutylamino-6-ndodecylamino-1,3,5-triazine (Table I, No. 1) are slowly added to this mixture and the whole is then stirred tor 45 minutes. The homogeneous mass so obtained is worked on a glass surface with a spatula until the excess benzene has evaporated.

The mass obtained is heated for 45 minutes at and, after cooling, is again worked with a spatula.

A good grease which can be well worked up is obtained.

Similar results are obtained on using the melamine derivatives given in Table I with the addition of the thickeners usually employed for the particular purpose.

Example 11 99 parts of Z-diethylamino l-dibutylaniino-fi-d1ihexylamino-1,3,5-triazine (Table I, No. 13) and 1 part of iminodibenzyl are stirred together until the latter has completely dissolved. The mixture obtained has improved stability to oxidation compared with the pure triazine compound.

Similar results are obtained if antioxidants suitable for the intended use are added in amounts of 0.01 to 5% to the compounds given in Table I. As antioxidants may also be used didodecyl selenide or 1,l,3-tris-(4-hydr-oxy-5'-tert. butyl-Z-me-thylphenyl) butane.

Similar results are obtained if the compounds given in Table I are mixed with high pressure additives and antioxidants suitable [for the intended use in amounts of 0.01 to 5%.

Example 12 Example 13 99.8 par-ts of 2,4-bis-dibutylamino-6-ditetradecylamino 1,3,5-triazine (Table I, No. 18) and 0.2 part of benzotriazole are mixed. Compared with the pure triazine,

the mixture obtained has a less cdrrosive action in particular on copper and alloys thereof.

Example 14 I 1250 parts of 2,4-bis-dibutylamino-6-chloro-s-t1iazine and 1490 parts of amine Airmeen 2C (composition given below) are stirred in a 5 litre round flask under an atmosphere of nitrogen. 150 parts of pulverized sodium hydroxide are added. Due to the exothermic reaction, the temperature rises to 135. The whole is then stirred at 130 bath temperature for 20 hours, then washed with water at 90 until the pH is 7-8 and it is tree of chlorine ions, after which it is filtered cold. Yield 87%. In this example, the filtrate contains 0.3% of secondary and primary amines and 1.65% of tertiary amines. Depending on the composition of the amine mixture, the filtrate is free from primary, secondary and tertiary amines.

The amine used in this and in the following examples is a technical product which consists of 85.6% secondary amines of average molecular weight of 423, 6.6% primary amines of average molecular weight of 220 and 7.8% tertiary amines of average molecular weight of 626.

The following alkyl radicals are present in the amine sample used, in the following amounts, in percent by WClglh-t: C 8%; C10, 9%; C12, C14, C16, 8%; C 10%; unsaturated alkyl 0%.

This amine mixture is referred to, hereinafter, for the sake of brevity, as Armeen 20, under which name the same is sold.

From this it can be seen that [for the reaction of 35.5 parts of labile chlorine, 415.7 rparts of this amine mixture are necessary. However, each batch of Armeen 2C must be analysed before use because the composition of the commercial product varies slightly. Depending on the special purpose, Armeen 2 0 can be fractioned by distillation.

Example 250 parts of the condensation prod-uct described in Example 14 from 2,4-bis-di-butylamino-6-chloro-2-triazine and Armeen which, in this case, contains 1.6% of secondary amines of average molecular weight of 423 and 1.6% of tertiary amines of average molecular Weight of 626, are diluted with 750 parts of cyclohexane and stirred in a very quickly rotating mixing apparatus for 30 minutes at 40-45 with 110 parts of an acid-pretreated montmorillo-nite as purifying agent. This acid pretreated montmorillonite is sold under such tradenarnes as Tonsil AC and Celite FC. The mixture is filtered and the filtrate is then treated again with 90 parts of Tonsil AC under the same conditions and again filtered. 'I he resident cyclohexane is removed from the filtrate by distillation and heating for 1 hour at 230 under 0.1 pressure. 217 parts of an almost colourless clear liquid are obtained, the total amine content of which is lower than 0.1%, which is the sensitivity limit of the potentiometric determination used.

This purification can also be per-formed at 60-70 and also at 20-25 Alkanes such as hexane can also be used instead of cyclohexane. In cases in which the tree amine content or the crude product is very low, Tonsil AC can also be used without solvent.

Example 16 50 parts of the condensation product described in Example 14 from 2,4-bis-dibutylarnino-6-chloro-s-triazine and Armeen 2C which contains 1.2% of secondary amines (average molecular weight 423) and 1.0% of tertiary amines (average molecular weight 626) are diluted with 500 parts of cyclohexane and very quickly stirred with 30 parts of Celite FC (adsorption earth, Messrs. Johns- Manville, U.S.A.), then filtered and again treated with fresh Celite FC until the product is free from amines. It is also possible to remove small amounts of free amines by using the hydrogen form of organic ion exchangers such as Amberlite IR 120. Here, too, hexane and methylcyclohexane can be used as diluents. Sometimes this treatment must be repeated until the end product contains no more free amines.

Example 17 650 parts of the condensation product described in Example 14 from 2,4-bis-dibutylamino-6-chloro-s-triazine and Armeen 2C which contains 0.3% secondary amines (average molecular weight 423) and 1.6 tertiary amines (average molecular weight 626), are distilled at 0.007 mm. pressure. The main fraction of 422 parts contains 0.15% of secondary amines and 1.25% of tertiary amines. The distillate is diluted with double the amount of cyclohexane and treated three times with 42 parts of Tonsil AC each time. Potentiometric analysis of the end product shows a total content of free amines of less than 0.1%, which is the sensitivity of the method. The content of secondary amines, which can be determined photo metrically, is 0.01% or less, which again corresponds to the sensitivity of the method used.

Example 18 200 parts of the condensation product described in Example 14 from 2,4-bis-dibutyl amino-6-chl-oro-s-triazine and Armeen 2C which contains 1.6% secondary amines (average molecular weight 423) and 1.6% tertiary amines (average molecular weight 626) are extracted with 50 parts of acetic acid and then extracted four times, with, in all, 110 parts of glacial acetic acid, washed neutral with water, filtered and dried. 165.2 parts of a product are obtained which contains less than 0.1% of free amine. In a similar way, the free amines which may be present in the triazines produced in the other examples, can be selectively extracted.

Example 19 97 parts of 2,4bis-dibutylamino-6-di(C H )-amino- 1,3,5-triazine (Table 1, No. 18) wherein x has a mean value of 14) and 3 parts of polymer of methacrylic acid ester, in particular poly-2-ethyl hexyl-methacrylate (HF 825 of Messrs. Rohm & Haas Co., Philadelphia, Pa., U.S.A.), are homogeneously mixed by stirring. This mixture has a lower solidification point than the pure 2,4- bis-dibutylamino-6-ditetradecylamino-l,3,5-triazine.

Example 20 250 parts of a condensation product from 2,4-bis-diethylamino-6-chloro-s-triazine and Armeen 20 which contains 1.0% secondary amines (average molecular weight 423) and 0.9% tertiary amines (average molecular weight 626) are diluted with 750 parts of cyclohexane and treated with Tonsil AC (110 parts) exactly as described in Example 15. The filtrate obtained is also treated with parts of Tonsil AC. 220.5 parts of an amine-free product are obtained. With the same bleaching earth, other s-triazines of Table I such as, e.g. Nos. 12, 16, 21, 24, 25 and 28 can be purified free of amines. Here also, hexane can be used as diluent instead of cyclohexane.

The following Tables I and Ia contain examples of N,N,N-substituted melamines useable according to the invention of the general formula They are produced by reacting cyanuric chloride in steps with the primary and secondary organic amines corresponding to X, Y and Z according to the method described in detail in Example 1. Column 5 of Table I shows the yield attained in the last step in percentage of the theoretical, columns 6 and 7 give the boiling point of the compounds under reduced pressure, column 8 shows the refractive index and column 9 the molecular weight of the compounds.

Table II shows the physical data of the compounds from which the suitability of these stable, difiicult to volatilize melamine derivatives as hydraulic liquids and/ or lubricants can be seen. Columns 2 and 3 give the viscosity measured at F. (=37.8 C.) and 210 F. (988 C.), and column 4 shows the so-called ASTM slope.

The meaning of the ASTM slope is as follows: If in a co-ordinate system, the temperature (in degrees Fahrenheit) is given as the abscissa and the natural log of the viscosity (in centistokes) is given as ordinate, then a plot is formed which, for practical purposes, can be regarded as straight. Thus, the viscosity for the whole temperature range can be interpolated from two points determined by experiment (conventionally the viscosities at 100 F. and 210 F. are determined). The slope of this plot is a standard for the dependency of the viscosity on temperature. Therefore, the ASTM slope is the quotient of the ordinate over the abscissa of the two points measured in cm. which are obtained by plotting the actual viscosity values at various temperatures in the ASTM chart. The ASTM Standard Viscosity-Temperature Charts for liquid petroleum products (Method D 341) are stand- 12 ard graphs which are in close resemblance to the coordinate system described above.

The lower the figure shown for a liquid in this ASTM slope the better suited it is as lubricant. A value of over 1.0 means that the liquid in question is not very suitable. ASTM is an abbreviation for American Society for Testing Materials, 1916 Race Street, Philadelphia, Pa, U.S.A.

Columns 5 and 6 show the loss in weight in percentage within 6 hours incurred by a sample of 25 cc. on heating to 380 or 400 C. in a glass test tube of about 25 mm. diameter with simultaneous introduction of nitrogen (2 litres per hour).

Column 7 shows the alteration in the viscosity in percentage measured at 210 F. incurred by the sample on 15 heating for 6 hours as described above.

TAB LE I B .P. at No X Y Z Percent nD MW C mm. Hg

N(C2H5)2 N(C H NHC I-I 90. 205-7 0. 02 1. 4980 462 N (02115) 2 N (C4Hg) 2 NH C H 93. 3 220 0. 02 1. 5055 546 N(C4Hq)2 N(C4H9)2 NHCBHM 75. 4 208-10 0. 03 1. 4969 462 4 9)2 N( 4 9)2 NHC1zI-I25 88. 7 204-15 0. 03 1. 4933 518 5 N 0-4119 2 N 04H.) 2 NHCIQH37 77. 0 266-70 0. 02 1. 4905 662 6 N(C4H9)2 N(C4H9)2 NH- 92. 6 190-99 0. 01 1. 5118 432 7 N(C4Ho)z N(O4H9)2 NHCHzCHOJzIn 85. 0 173-85 0. 01 1. 5000 462 02H 8 N(C4H9)z N(C4Hg)g N 83. 9 187-98 0.02 1. 5083 460 OHa 9 N (04119) 3 N (C4Hp) N 88. 8 186-06 0. 01 1. 4927 476 CsHn 0 Ha C H2 10 N(C4H9)z N(C Hn)g CH 92. 5 178-82 0. 02 1. 5112 418 C Hg C 2 11 N(C4Hn)2 N(C4Hn)2 N(C5H13)q 92. 9 198-207 0. 02 1. 4921 518 CH3 12 N (C2115) 7 N(C9H5) z N 92. 3 162-67 0. 02 1. 5023 364 C sHn 13 N(C2H5)a N(C4Ho)2 N(CBH13)2 93. 0 202-4 0. 02 1. 4937 462 0 H 14 N(C2H5)z N(C4H9)2 N 91. 5 210 0. 01 1. 4903 560 OnHn C 112 15 N(C4H9)2 N(C4Hv)2 4 N (CH2)4 93. 5 178-80 0. 002 1. 5123 432 16 N(C2H5)2 N(C4Hn)2 N(C14 )2 8- 0 0- 03 1- 4856 686 17 N(C2H5)2 N(C2H5)2 I I(C14]129)2 93- 0 220 0. 01 1. 4867 630 18 N(C4H9)2 N(C4Ho)2 N(O14 29)2 11 2 1- 5855 742 0 Ha 19 N N(C2H5)2 N(C4H9)2 95. 4 161-3 0. 04 1. 4967 420 O EH17 20 N(CH5)z N(C H5)z N(C8H17)2 94. 5 190 0. 06 1. 4931 462 21 .V N(CH5)z N(C2H5)2 N(Ci2H25)2 96. 5 200 0. 02 1. 4897 574 22 N(C4Ho)2 N(C4He)z N(C 8Hl7)2 98.1 200 0.07 1. 4908 574 23 N(C4Ho)z N(C4H9)2 N(C12H25)a 98. 0 200 0- 05 1. 4866 686 24- N(CH3)2 N(C4Hw)2 N(C12 25)2 97. 4 200 0. 06 1. 4892 602 ANN...

TABLE I-Continued B.P. at No X Y Z Percent 11D MW mm. Hg

25 M 3): (C4Hs)a N( 01411102 96. 7 200 0. 1. 4876 658 26 N(C2H5)a N (C4HD)2 N (081111): 95. 3 200 0.03 1. 4924 518 27 N(CaH )a N(C4Hn)2 N(C12H25)2 94. 6 200 0.03 1. 4872 630 CH2 CH1 28 N (CHm I T(C1141 .[2n)2 N\ )CHM 97. 1 240 0.05 1. 5000 598 0 Hz 0 H:

= A mixture of straight chain alkyl groups, the mean carbon number of which corresponds to about 14.

TABLE II Viscosity in centistokes at Loss in weight after 6 hours at Change in viscosity after N o. ASTM slope 6 hours in 100 F. 210 F. centistokes in (37.8" G.) (988 0.) 0. Percent peiirae t at The lubricity of 5 representative compositions of matter according to the invention and of di-3,5,5-trimethylhexyl sebacate as comparison was measured in a Shell 4 ball apparatus. The apparatus was run for 30 minutes at 1450 revolutions per minute under a 40 kg. load and using half inch grade A S.K.F. steel balls. The starting temperature was about 40 C. The results are summarised in the following Table III:

Scar diameter in mm. 5 0.604 13 0.569 0.599 0.511 18 0.546

Scar diameter Substance used, No. (from Table I):-Oont. in mm.

di-3,5,5-trimethyl-hexyl sebacate 0.896 di-Z-ethyl-hexyl sebacate 0.850 di-Z-ethyl-hexyl adipate 0.915 methyl phenyl silicone* 1.953

*In this test lubrication ceased even after 215 minutes.

Each of the values given above is the average from three measurements.

As can be seen from the above, the compounds according to theinvention can be used direct for the lubrication of solid surfaces. The following test illustrates the applicability of the composition of matter mentioned for the lubrication of glass surfaces:

When the compound No. 16 in Table I is applied to tacked is expressed in mg./cm.

the ground glass surface of a stopper and the stopper is entered into the correspondingly formed orifice of a glass flask, the stopper is held fast and the flask is rotated around it at least 39x10 times at room temperature for 130 hours, without sticking due to glass to glass friction. If, instead of the compound No. 16 of Table I, a commercially available and widely used silicone high vacuum fat is employed under the same condition then the rotated flask becomes stuck after 24 hours.

Example 21 88 g. (100 ml.) of the product obtained according to Example 15, first paragraph, which was hydrogenated cold with H over palladium to remove any residual olefinic double bonds, is heated to 260 for 6 hours. At the same time, 5000 parts by volume of air per hour are passed through the liquid. The degree by which the metal is at- The change of viscosity which occurs during the heating is measured at 378 and given in percentages. The acid thus formed is measured at the end of the experiment and expressed in mg. KOH/ g. The formation of sludge, i.e. the undissolved matter dispersed in the liquid reaction mixture, is determined by filtration and weighing and expressed in mg./ 100 ml. of the reaction product. The insoluble coating adhering to the Walls of the reaction vessel, which forms during the oxidation, is designated as a varnish below and its amount was estimated visually.

The following data were obtained by carrying out the above example without use of an antioxidant additive:

Change in viscosity (percent) +160 Acid concentration 5.06 Sludge 11.4 Metal attack 0.08 Varnish Very heavy (a) 88 g. (100 ml.) of the product obtained according to Example 15, first paragraph, which was hydrogenated cold with H over palladium to remove any residual olefinic double bonds was mixed with 1 g. of 1,1,3-tri-(2'- methyl-4'-hydroxy-5'-tert. butylphenyl)-butane and further treated as described above. The resulting product afforded the following data in the above test:

Change in viscosity (percent) +6.4 Acid concentration 0.45 Sludge 8.8 Metal attack 0.06 Varnish Moderate (b) 88 g. (100 ml.) of the product obtained according to Example 15, first paragraph, and 1 g. of 2,6-di-(tert. butyl)-4-methyl-1-hydroxybenzene treated as described above, afforded the following data in the above test:

Change in viscosity (percent) +5.6 Acid concentration 0.55 Sludge 20.1 Metal attack 0.13 Varnish Slight (c) 88 g. (100 ml.) of the product obtained according to Example 15, first paragraph, and 1 g. of 2-tert. octyliminodibenzyl treated as described above, alforded the (d) 88 lg. 100 ml.) of the product obtained according to Example 15, first paragraph, plus 1 g. of 5-ethyl-10,10- diphenyl-phenosilazine and 1 g. of N-phenyl-a-naphthyl- 1t) amine treated as described above, afforded the following values in the above test:

Change in viscosity (percent) +5.1 Acid concentration 0.45 Sludge 9.6 Metal attack 0.12 Varnish Very slight (e) 88 g. ml.) of the product obtained according to Example 15, first paragraph, and 1 g. of didodecyl selenide treated :as described, afforded the following values in the above test:

Change in viscosity (percent) +3.1

Acid concentration 0.43

Sludge 25,6

Metal attack 0.13

Varnish Heavy Example 22 60 parts of the product obtained according to Example 15, first paragraph, which was hydrogenated cold with .H over palladium to remove any residual olefinic double wherein X is a di (lower alkyl) amino in which each alkyl radical has from 1 to 4 carbon atoms,

Y is a di (lower alkyl) amino in which each alkyl radical has from 1 to 4 carbon atoms, R is a member selected from the group consisting of hy= drogen and alkyl of maximally 14 carbon atoms, I R is a member selected from the group consisting of alkyl of at least 6 and maximally 18 carbon atoms and cyclohexyl, the sum of the total number of alkyl carbon atoms in R and R being at least 8 and not more than 28 when R is alkyl, and

R and R taken together can be a member selected from the group consisting of (CH and (CH 2. A compound of the formula wherein x represents a mean value of 14.

3. A compound of the formula ITI(CXHIX+I)R I r t (HDCQ)BN O C (C4 e)2 wherein x represents a mean Value of 14.

4. A compound of the formula I?T( C xH2+1 I o wherein x represents a mean value of 14.

17 18 5. A compound of the formula 8. A compound of the formula NH-CISHU A N- o H (I) 12 2.5)2 17 \lfiI oC4)2 C CN(C4H9)2 a N (H0C4)2N-"C\ C- (C a)2 References Cited by the Examiner UNITED STATES PATENTS 2,276,162 3/1942 Colin 25250 A compound of the formula 2,279,561 4/1942 Dietrich 252 50 2,714,057 7/1955 Chenicck 2525O X I 2,909,421 10/1959 Gysin et al 260-249.6 X NO(12H2s)z 2,980,637 4/ 1961 Culbertson et a1. 260249.6 3,050,522 8/1962 Coates et a1. 260-249.6 3,055 ,897 9/ 1962 Schwartz et a1. 260249.6 (HsG2)2N( J )N(CzH5)2 2O FOREIGN PATENTS 552,928 2/1958 Canada.

OTHER REFERENCES Campbell et al., Jour. Org. Chem., vol. 26 (Aug. 1961),

7. A compound of the formula pp. 27 869.

Smolen et al., The Chemistry of Heterocyclic Compounds, S-Triazenes and Derivatives, Interscience Pub- ITIACBHU), lishers Inc., New York (1961), pp. 373-78. WALTER A. MODANCE, Primary Examiner. JOSEPH R. LIBERMAN, NICHOLAS S. RIZZO, JOHN eOm 0 G-N(O4Hs)2 D. RANDOLPH, Examiners.

N T. D. TAYLOR, I. M. FORD, Assistant Examiners. 

1. A COMPOUND OF THE FORMULA 